Structure of Polymer Brushes in Cylindrical Tubes: A Molecular Dynamics Simulation

TL;DR

This study uses Molecular Dynamics simulations to explore how polymer brushes behave inside cylindrical pores, revealing how chain length, grafting density, and pore size influence brush height and structure, with implications for theoretical models.

Contribution

It provides new insights into the behavior of polymer brushes in cylindrical geometries, comparing simulation results with existing theories for flat and concave substrates.

Findings

Brush height can exceed that on flat surfaces in large pores.

Confinement compresses the brush in small pores.

Transition from mushroom to brush behavior depends on parameters.

Abstract

Molecular Dynamics simulations of a coarse-grained bead-spring model of flexible macromolecules tethered with one end to the surface of a cylindrical pore are presented. Chain length $N$ and grafting density $\sigma$ are varied over a wide range and the crossover from ``mushroom'' to ``brush'' behavior is studied for three pore diameters. The monomer density profile and the distribution of the free chain ends are computed and compared to the corresponding model of polymer brushes at flat substrates. It is found that there exists a regime of $N$ and $\sigma$ for large enough pore diameter where the brush height in the pore exceeds the brush height on the flat substrate, while for large enough $N$ and $\sigma$ (and small enough pore diameters) the opposite behavior occurs, i.e. the brush is compressed by confinement. These findings are used to discuss the corresponding theories on polymer brushes at concave substrates.